Issue 16, 2001

Coupled electron/proton transfer of galvinol attached to SAMs on gold electrodes

Abstract

The theory for a 1-electron, 1-proton redox couple with potential-dependent transfer coefficients is tested using a self-assembled monolayer with attached galvinol/galvinoxyl redox couples on a gold electrode. The potential dependence of the transfer coefficients is derived from the Marcus density-of-states model of heterogeneous electron transfer. The pKa of surface-attached galvinol is 11.3. The predicted asymmetry in kinetically controlled cyclic voltammograms is observed at pHs lower than 11. Apparent standard rate constants between pH 10 and 13 are fitted to the theory to yield a standard rate constant of 4.5 Ɨ 10 sāˆ’1 for the deprotonated galvinol/galvinoxyl radical redox couple; this standard rate constant is comparable to the standard rate constant for ferrocene/ferricenium with the same number of atoms linking the redox center to the electrode. Anomalous behavior is seen for the apparent standard rate constants at pHs between 7 and 9.

Article information

Article type
Paper
Submitted
09 Feb 2001
Accepted
29 Mar 2001
First published
15 May 2001

Phys. Chem. Chem. Phys., 2001,3, 3431-3436

Coupled electron/proton transfer of galvinol attached to SAMs on gold electrodes

H. O. Finklea and R. M. Haddox, Phys. Chem. Chem. Phys., 2001, 3, 3431 DOI: 10.1039/B101325O

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